Organic-inorganic perovskite light-emitting devices have recently emerged as a reliable light source. Here, we developed a Single Layer Perovskite Light-Emitting Electrochemical Cells (SL-PeLEC) with laminated free-standing Carbon Nanotube Sheet (CNT) sheets as an effective charge electron injecting cathode electrode. The structure consists of bottom ITO-on-glass as a transparent electrode, the composite of CsPbBr3:PEO:LiPF6 with additive ionic salt as an emitting layer (EML) and 5 layers of CNT aerogel sheets as a top laminated cathode . Utilizing CNT free standing sheets laminated right on top of perovskite thin film in this simple single layer configuration has multiple benefits. Such CNT top cathode does not show any chemical degradation by reaction with halogens from perovskite, which is detrimental for metallic cathodes. Moreover, the formation of an internal p-i-n junction in perovskite EML composite layer by ionic migration under applied voltage bias and electric double layer (EDL) formation at each electrode interface is beneficially effecting CNT sheets by Li+ ionic doping and raises their Fermi level, further enhancing electron injection. Besides, inspired by successes of ionic additives in LECs and electrochemical doping of perovskite with alkali metals, we leveraged a lithium salt, LiPF6, within a CsPbBr3:PEO composite matrix to achieve optimal ionic redistribution and doping effects in this SL-PeLEC. Although initially CNT electrode has slightly high sheet resistance, the SL-PeLEC device has a low turn-on voltage of 2.6v and a maximum luminance intensity of 530 cd/m2, confirming the n-doping increased conductivity. This work provides a unique route toward flexible and bright perovskite LECs with stable and transparent CNT electrodes that can have injection efficiency tuned by poling induced ionic EDL-doping.
One major hurdle in the progress of hyperbolic metamaterials (HMMs) is their lossy nature due to the metal constituent. In this work, we design a gain-assisted active HMM utilizing the recently emerged, solution-processed perovskite gain material. Our HMM is consisted of MAPbI3 perovskite and Au subwavelength multi-layer. We theoretically and experimentally investigate the strong emission polarization anisotropy that is unique to HMMs. Our work opens the way towards applications such as high-speed light emission, super resolution imaging and lithography, electro-optical modulators and perfect light absorbers.
Here we report theoretical and experimental results for a high-Q cavity based on nanoimprinted perovskite film. We reveal that bound state in the continuum transformed into a resonant state due to leakage into substrate leads to significant enhancement of the photoluminescence signal of the perovskite cavity.
The hybrid (organo-inorganic) lead-halide perovskites revolutionized the field of solar cell research due to the impressive power conversion efficiencies of up to 21% recently reported in perovskite based solar cells. This talk will present first the general concepts of excitonic photovoltaics, as compared to conventional Si-type solar cells, asking a question: is hybrid perovskite PV an excitonic solar cell or not? Do we need excitons dissociation at D-A interfaces or CNT charge collectors? Then I will show our recent experimental results on the fast spectroscopy of excitons, magnetic field effect on generation of correlated (e-h) pairs. Also will discuss our Hall effect results, that allows to evaluate intrinsic charge carrier transport and direct measurements of mobility in these materials performed for the first time in steady-state dc transport regime. From these measurements, we have obtained the electron-hole recombination coefficient, the carrier diffusion length and lifetime. Our main results include the intrinsic Hall carrier mobility reaching up to 60 cm2V-1s-1 in perovskite single crystals, carrier lifetimes of up to 3 ms (surprisingly too long!), and carrier diffusion lengths as long as 650 μm (huge if compared to organic and even best inorganic materials). Our results also demonstrate that photocarrier recombination in these disordered solution-processed perovskites is as weak as in the best (high-purity single crystals) of conventional direct-band inorganic semiconductors. Moreover, as we show in our experiment, carrier trapping in perovskites is also strongly suppressed, which accounts for such long carrier lifetimes and diffusion lengths, significantly longer than similar parameters in the best inorganic semiconductors, such e.g. as GaAs. All these remarkable transport properties of hybrid perovskites need to be understood from fundamental physics point of view. Looks like we need some new concepts to explain the mysterious properties of “protected” hybrid perovskites. We suggest that some of this unusual properties can be attributed to a special type of “dipole rotational polaron” formed in their lattice due to interactions of charge with methyl-ammonium organic dipoles, each of 2.3 Debye. Examples of perovskite solar cell with transparent CNT charge collectors will demonstrated the 3 D charge collection in the monolithic tandems of perovskite PV with other dissimilar materials PVs, such as OPV and inorganic PV. We describe the pioneering methods to create highly transparent CNT sheets by dry lamination from vertically alligned CVD forests of MWCNTs. Transparency can be further increased by converting CNT aerogels into locally collapsed meshs with micron scale oppenings by spraying Ag nanowires, which lowers sheet resistance to values of Rsh< 40 ohm/sq. such AgNW@CNT transparent sheets are ideal interlayers in three terminal tandems of perovskite PV with polymeric OPV and/or inorganic solar cells. We show that nanoimprinting can further improve the performance of perovskite photodetectors and optoelectronic devices
Among the various organic photovoltaic devices, the conjugated polymer/fullerene approach has drawn the most research interest. The performance of these types of solar cells is greatly determined by the nanoscale morphology of the two components (donor/acceptor) and the molecular orientation/crystallinity in the photoactive layer. This article demonstrates our recent studies on the nanostructure geometry effects on the nanoimprint induced poly(3 hexylthiophene-2,5-diyl) (P3HT) chain alignment and photovoltaic performance. Out-of-plane and in-plane grazing incident X-ray diffractions are employed to characterize the chain orientations in P3HT nanogratings with different widths and heights. It is found that nanoimprint procedure changes the initial edge-on alignment in non-imprinted P3HT thin film to a vertical orientation which favors the hole transport, with an organization height H≥ 170 nm and width in the range of 60 nm≤ W< 210 nm. Samples with better aligned molecules lead to a larger crystallite sizes as well. Imprinted P3HT/[6,6]-penyl-C61-butyric-acid-methyl-ester (PCBM) solar cells show an increase in power conversion efficiency (PCE) with the decrease of nanostructure width, and with the increase of height and junction area. Devices with the highest PCE are made by the fully aligned and highest P3HT nanostructures (width w= 60 nm, height h= 170 nm), allowing for the most efficient charge separation, transport and light absorption. We believe this work will contribute to the optimal geometry design of nanoimprinted polymer solar cells.
The negative refraction inside two dimensional (2D) photonic crystals (PC) and homogeneous structures was studied numerically by inserting a point source inside the negative index part of these materials. The three-dimensional (3D) counterparts of these structures, the synthetic opal, were examined experimentally by infiltrating them with CdS quantum dots (QDs). Confocal microscopy measurements in which we tracked the infiltration of the QDs inside the opal indicate the focusing of light emitted by QDs, which can be due to negative refraction occurring at the opal/glass interface. The formation of a focus can be an indication of the negative refraction happening in these synthetic opals in the [111] direction in its higher photonic band, above the photonic band gap (PBG). This result is very promising because, until now, negative refraction has not been seen in 3D photonic crystals in the visible region of light. This result was made possible due to the use of infiltrated QDs as internal light sources inside the porous photonic crystal, which appears to be a very useful technique for the study of other negative-index materials (NIM) effects. Finally, the possibility of self-focusing of second harmonic by QD in nonlinear opal was developed.
In our work, we investigate photonic bandgap (PBG) structures coated by nonlinear covering as systems that are of
interest for possible applications in the all-optical adders and logical gates. Two principal schemes of an all-optical adder
based on the 1D PBG materials containing optically nonlinear layers are discussed. It is shown that the only nonlinear
layer covering linear photonic crystal gives effective signal control and signal processing. Theoretical estimations of the
adder cell parameters are made for Si/SiO2 photonic crystals covered with layers made from nonlinear doped glasses.
The calculated angular-frequency diagrams exhibited extremely sensitive areas inside the total reflection range, where
the weak nonlinearity leads to dramatic change in light reflection and transmission.
We report the observation of cathodoluminescence (CL) of organic multilayers of tris-(8-hydroxyquinoline) aluminium (Alq3) and 2- (4biphenyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD) deposited on ITO-coated glass, with and without hole transport layer and compare it with electroluminescence (EL) from similar devices. Excitation of the CL of such multilayer organic anodes was accomplished by low energy electrons field emitted by single walled carbon nanotube
cathodes. The dependence of CL spectrum and intensity on voltage (V), current (I), type of transport layer and the cathode-anode geometry has been studied. We propose carbon nanotubes as efficient cathodes for stable CL emission from multi-layer anodes at small cathode-anode separations. The role of hole-transport layer is also discussed.
We report a novel type of nanocomposite of conjugated polymer (regio-regular polythiophene) with infrared-sensitive, PbSe quantum dots (QD), which have size-tunable lowest-energy absorption bands between 0.3 and 1 eV. Thin film devices show very good diode characteristics and sizable photovoltaic response with an open circuit voltage, Voc, of ~ 0.3-0.4 V and short circuit current density, Jsc, of ~ 0.2mA/cm2, which is significantly higher than recently reported in PbS QD-based devices. This is the evidence of a quite efficient photoinduced charge transfer between the polymer and QD, with infrared sensitivity. Photocurrent under reverse bias is significantly enhanced to Jph ~ 1 mA/cm2 indicating that the polythiophene/PbSe QD system can be used as effective infrared photodetectors. Detailed spectroscopic studies of photoresponse over a wide spectral range are presented. Quenching of photoluminescence by PbSe QDs has also been studied to gain more understanding of energy and charge transfer in this system.
We present this detailed study of a postproduction heat treatment of flexible organic solar cells based on regio-regular (RR) P3HT:PCBM composite in a wide temperature range from 75°C to 150°C. The efficiency of the photovoltaic device was significantly improved by postproduction heat treatment and both optimal annealing temperature and time dependencies were determined. Optimized parameters yielded >3% efficiency for devices on glass substrates and, using these optimized parameters, an efficiency of >2% was found for devices fabricated on flexible substrates. The optimal phase separation of PCBM and RR-P3HT into bi-continuous network structure occurs within a very short period of time and are very stable. We found that optimal concentration of PCBM in a RR-P3HT matrix is rather low, only 34 w.%. We show the performance of plastic solar cells fabricated on flexible substrates (ITO coated PET) using these optimized heat treatment parameters.
The study is devoted to closed and transferred electromagnetic field in one-dimensional both transparent photonic crystals and crystals containing layers which absorb irradiation alternated by transparent layers. General theory of irrdiation closed inside the crystal is developed both in case transparent and adsorbing metallic photonic crystals in wide frequency range. True or absolute photonic gaps existing in the total reflection angle range are analyzed on the base of internal problem's analytical solution for 1D layered superlattices. We have investigated the frequency-angle diagrams for TM and TE photonic spectra trapped inside the whole reflection range for mesoscopic and macroscopic hierarchical 1D photonic crystals of varied topologies, geometry and materials. The effects of double refraction in binary multi-layered system and photon localization in finite periodic layered structures are investigated analytically and numerically. Energy storage and energy decay time in photonic crystals are considered with account for field amplitudes distribution inside the structure and angular band kinetics. The effect of sharp focusing of the butt-end emission for closed electromagnetic waves in 1D photonic crystals is discussed.
Photonic crystals (PC) are a class of artificial structures with a periodic dielectric function. PCs can be a laboratory for testing fundamental processes involving interactions of radiation with matter in novel conditions. We have studied the optical properties of opal PCs that are infiltrated with highly polarizable media such as j-aggregates of cyanine dyes. Opals are self-assembled structures of silica spheres. We report our studies on clarifying the relationship between a polaritonic gap and a photonic stop band (Bragg gap) when they resonantly coexist in the same structure. Infiltration of opal with polarizable molecules combines the polaritonic and Bragg diffractive effects. Both effects exist independently when the Bragg (at ω = ωB) and polaritonic (ω = ωT) resonances are well separated in frequency. A completely different situation occurs when ωT ≈ωB. Such a condition was achieved in opals that were infiltrated with J-aggregates of cyanine dyes that have large Rabi frequency. Our measurements show some dramatic changes in the shape of the reflectivity plateaus, which are due to the interplay between the photonic band gap and the polaritonic gap. The experimental results on reflectivity and its dependence on the light propagation angle and concentration of the cyanie dyes are in agreement with the theoretical calculations.
Recent studies of lasing and stimulated emission in luminescent (pi) -conjugated polymers performed by our group are presented. Optical properties of cylindrical, high-Q, polymer microcavities are discussed. The emission spectra of plastic microring and microdisk lasers were measured and analyzed. Cylindrical light emitting polymer microdiodes, as possible candidates for electrically-driven plastic lasers have been fabricated. Stimulated emission and lasing were also demonstrated for polymer solutions infiltrated in opal photonic crystals. In addition, two unusual regimes of stimulated emission characterized by narrow laser-like spectral lines were found in thin waveguiding polymer films. These regimes may be associated with random optical feedback introduced by light scattering inside the polymer films and amplified Raman scattering, respectively.
The general features of charge transfer processes fullerene/conducting polymer (CP) systems, such as energetics of photoinduced charge transfer (PCT) between C60 and CP (pi) - electronic states, geometry of (pi) -(pi) overlapping and the role of self-trapping effects to polaronic states on C60 and CP chains on the PCT dynamics are analyzed. Persistent photoconductivity and electroluminescence quenching recently found in C60/CP composites additionally to photoconductivity enhancement and photoluminescence quenching observed earlier, indicate that photogenerated C60 radicals may be extremely long living in CP matrices, due to multicharging of C60 as suggested by us accompanied with deep self-trapping to polaron/bipolaron states. The anisotropy of PCT is proposed to arise due to orientational modulation of overlapping between polaronic rings on C60 and CP which strongly suppresses back recombination. The strategy to increase the efficiency of C60CP donor-acceptor (DA) photocells by improving PCT is analyzed, particularly considering multilayered structures with polarization barriers at interfaces, and increased intralayer mobilities of carriers. To increase the efficiency of photons collection in photocells we suggest three layered D-M-A structures, with molecular 'photon pump' layers strongly absorbing photons. The prospects for novel photonic applications of various C60CP systems, such as NLO devices and photomodulated field effect transistors (FETs) are discussed and illustrated by the newest results. New results on superconductivity of C60/CP upon alkali metal doping are presented, and exciting possibilities for novel superconducting phases in this system are discussed.
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